WO2018036425A1 - Matériau composite caoutchouc modifié à base de graphène 3d et son procédé de préparation - Google Patents

Matériau composite caoutchouc modifié à base de graphène 3d et son procédé de préparation Download PDF

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WO2018036425A1
WO2018036425A1 PCT/CN2017/098066 CN2017098066W WO2018036425A1 WO 2018036425 A1 WO2018036425 A1 WO 2018036425A1 CN 2017098066 W CN2017098066 W CN 2017098066W WO 2018036425 A1 WO2018036425 A1 WO 2018036425A1
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parts
rubber
dimensional graphene
graphene
accelerator
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PCT/CN2017/098066
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Chinese (zh)
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段曦东
赵涛楠
毛志浩
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广东纳路纳米科技有限公司
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Publication of WO2018036425A1 publication Critical patent/WO2018036425A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of materials, in particular to a rubber composite material based on three-dimensional graphene modification and preparation thereof.
  • Rubber is the basic raw material of the rubber industry. It has the advantages of light weight, corrosion resistance and easy scale production. It can adjust the electrical and mechanical properties of materials according to the needs of use. It is used in the fields of tire, electronics, daily chemical and aerospace. It is becoming more and more widespread. And these applications require rubber products with excellent antistatic, electrical or thermal, mechanical and gas barrier properties.
  • the composite rubber is made of rubber as a matrix and is filled with conductive and thermally conductive fillers to impart certain electrical and thermal conductivity to the rubber.
  • the electrical conductivity of the composite conductive rubber mainly depends on the electrical conductivity of the filler and the uniform dispersion of the filler in the rubber matrix.
  • Commonly used fillers are carbon black, graphite, graphite fiber, and metal powder. Among them, carbon black is the most widely used conductive filler. When the amount of carbon black reaches a critical value, the electrical conductivity of the rubber is significantly improved.
  • the composite conductive rubber needs to achieve high electrical properties, the amount of carbon black to be added is very large, which affects the viscosity and processing properties of the rubber matrix material, and its application is limited.
  • Nano-sized fillers such as carbon fibers, carbon nanotubes, etc. can achieve higher electrical properties with low loading, but the agglomeration problem makes it difficult to achieve good dispersion in the matrix, and there are cost problems that limit the development of its application.
  • the rubber is a poor conductor of heat, and the generated heat cannot be conducted out in time, causing heat to accumulate inside the rubber product.
  • the temperature is too high, the performance of the product is lowered, and the service life of the product is affected.
  • Rubber modification is an effective way to improve the thermal conductivity of materials, and nanomaterials have great potential for rubber reinforcement and functionalization due to their unique molecular structure and properties.
  • the present invention adopts the following technical solutions:
  • the three-dimensional graphene-modified rubber composite material of the present invention comprises, by weight, 100 parts by weight of rubber, 0.01-5 parts of three-dimensional graphene, 0.5 to 5 parts of vulcanizing agent, and 8 to 12 parts of a rubber compounding agent.
  • the rubber comprises at least one of natural rubber, silicone rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, isoprene rubber, butane rubber, nitrile rubber, ethylene propylene rubber, and neoprene rubber.
  • the three-dimensional graphene has a three-dimensional interconnected porous network of submicron to several micrometers.
  • the vulcanizing agent includes at least one of sulfur, a peroxide, a metal oxide, and a sulfur-containing organic substance.
  • the rubber compounding agent includes: a promoting auxiliary agent, an accelerator, and an antioxidant.
  • promotion aid is at least one of zinc oxide or stearic acid
  • the accelerator includes at least one of the accelerator D, the accelerator DM, the accelerator TMTD, the accelerator CZ, the accelerator BZ, and the accelerator MBT;
  • the antioxidant includes at least one of an antioxidant RD, an antioxidant 4010, an antioxidant 124, and an antioxidant DNP.
  • the rubber compounding agent comprises, in parts by mass, 2 parts of stearic acid, 5 parts of zinc oxide, 1 to 2 parts of a promoter, and 1 to 3 parts of an antioxidant.
  • the invention is based on a method for preparing a three-dimensional graphene-modified rubber composite material, comprising:
  • Step 1) preparing graphene oxide by a modified Hummers method
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1-2 mg/ml, and then transferred to a reaction vessel at 160-200 ° C for 20-24 hours, washed with water. , got To three-dimensional reduction of graphene oxide hydrogel, freeze-drying;
  • Step 3) The rubber, the three-dimensional graphene obtained in the step 2), the rubber compounding agent and the vulcanizing agent are sequentially added to the open mill, kneaded at 40-90 ° C for 10-30 min, and the rubber mixture is allowed to stand for 16-24 h, The vulcanization machine is vulcanized, and the vulcanization condition is vulcanized at 140-170 ° C for 10-40 min to obtain a three-dimensional graphene-modified rubber composite material.
  • the improved Hummers method produces graphene oxide, which is divided into pre-oxidation, oxidation and stripping;
  • the pre-oxidation is: mixing 1 part of natural graphite, 3-10 parts of concentrated sulfuric acid, 0.5-0.9 parts of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, reacting for 6 h, using super Purified pure water to neutral to obtain pre-oxidized graphite;
  • the oxidation is: at 0 ° C, the pre-oxidized graphite is mixed with 6-20 parts of concentrated sulfuric acid, and 1-3 parts of KMnO 4 are gradually added under stirring, and the temperature of the mixture is controlled to be below 20 ° C in the process.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20-50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 40-150 parts of ultrapure water was added to complete the reaction. Next, 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions, and the resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral;
  • the peeling In order to peel off the graphite oxide, the obtained product was ultrasonicated for 30 min with a 400 W cell pulverizer, and the supernatant was centrifuged at 13,000 rpm, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide.
  • the three-dimensional graphene of the invention has a self-supporting structure, avoids agglomeration and has good dispersibility in rubber; the three-dimensional graphene has excellent electrical, thermal and mechanical properties, and is easy to be in close contact with the substrate of the invention, greatly increasing The electrical conductivity, wear resistance, heat resistance and mechanical strength of the rubber product; the invention has simple preparation process, low production cost, no environmental pollution, and is easy to realize large-scale industrial production.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 6 parts of concentrated sulfuric acid, 0.7 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 hours, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.8 mg/ml, and then transferred to a reaction vessel at 200 ° C for 20 h, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of butadiene rubber, 0.1 part of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of accelerator CZ, 1.5 parts of antioxidant RD, 1.5 parts of sulfur are sequentially added to the open mill, 50 After mixing for 20 min at ° C, the rubber mixture was allowed to stand for 24 h, and then vulcanized on a flat vulcanizer. The vulcanization conditions were 151 ° C for 25 min to obtain a three-dimensional graphene-modified butadiene rubber composite.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 5 parts of concentrated sulfuric acid, 0.6 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 8 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 30 parts of ultrapure water was added, stirring was continued for 15 min, and finally 50 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.5 mg/ml, and then transferred to a reaction vessel at 180 ° C for 20 h, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of styrene-butadiene rubber, 0.2 parts of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator BZ, 1 part of antioxidant RD, 1 part of antioxidant 4010, 1 part of sulfur are sequentially added.
  • the mixture was kneaded at 50 ° C for 25 min, and the rubber mixture was allowed to stand for 18 h, and then vulcanized on a flat vulcanizer, and the vulcanization conditions were 150 ° C for 30 min to obtain a three-dimensional graphene-modified styrene-butadiene rubber composite material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 7 parts of concentrated sulfuric acid, 0.6 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 9 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20-50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 100 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.5 mg/ml, and then transferred to a reaction vessel at 180 ° C for 24 hours, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of nitrile rubber, 0.4 parts of three-dimensional graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator TMTD and 0.5 parts of accelerator MBT, 1 part of antioxidant RD and 1 part of antioxidant 4010 2 parts of sulfur were added to the open mill in turn, and kneaded at 40 ° C for 20 min. After the mixture was allowed to stand for 16 h, it was vulcanized on a flat vulcanizing machine, and the vulcanization conditions were 170 ° C for 16 min to obtain a three-dimensional graphene-modified nitrile rubber composite. material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation Mix 1 part of natural graphite, 3 parts of concentrated sulfuric acid, 0.5 part of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, react for 6 h, and wash with ultrapure water until neutral. oxidised graphite.
  • Pre-oxidized graphite was mixed with 8 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20 parts of ultrapure water was added, stirring was continued for 15 min, and finally 40 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1 mg/ml, and then transferred to a reaction vessel at 160 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3 100 parts of natural rubber, 0.6 parts of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 parts of accelerator TMTD, 1 part of accelerator CZ, 1 part of antioxidant RD, 1 part of antioxidant 4010, 0.5 parts of sulfur was sequentially added to the open mill, and kneaded at 50 ° C for 12 min. After the mixture was allowed to stand for 24 h, it was vulcanized on a flat vulcanizer, and the vulcanization conditions were 150 ° C for 40 min to obtain a three-dimensional graphene-modified natural rubber composite material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 9 parts of concentrated sulfuric acid, 0.9 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 hours, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 90 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 22 h, washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3 100 parts of butadiene rubber, 0.8 parts of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of accelerator CZ, 1.5 parts of antioxidant RD and 1 part of antioxidant 4010, 3 parts of sulfur are added to the open mill in turn, and kneaded at 60 ° C for 15 min. After the mixture is allowed to stand for 24 h, it is vulcanized and vulcanized on a flat vulcanizer. The condition was 151 ° C for 25 min to obtain a three-dimensional graphene-modified butadiene rubber composite.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation Mix 1 part of natural graphite, 8 parts of concentrated sulfuric acid, 0.8 parts of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, react for 6 h, and wash with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 35 parts of ultrapure water was added, stirring was continued for 15 min, and finally 90 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.8 mg/ml, and then transferred to a reaction vessel at 200 ° C for 24 hours, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of styrene-butadiene rubber, 1 part of 3D graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1.5 parts of accelerator BZ, 1 part of antioxidant RD and 1 part of antioxidant 4010, 2.5 parts of sulfur are sequentially added.
  • the mixture was kneaded at 50 ° C for 30 min, and the rubber mixture was allowed to stand for 24 h, and then vulcanized on a flat vulcanizing machine, and the vulcanization conditions were 150 ° C for 30 min to obtain a three-dimensional graphene-modified styrene-butadiene rubber composite material.
  • Step 1) Preparation of graphene oxide by modified Hummers method, which is divided into pre-oxidation, oxidation and Stripped.
  • Pre-oxidation 1 part by weight of natural graphite, 10 parts of concentrated sulfuric acid, 0.9 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 20 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 150 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3 100 parts of nitrile rubber, 2 parts of three-dimensional graphene, 5 parts of zinc oxide and 1 part of stearic acid, 1 part of accelerator TMTD and accelerator 1 part of MBT, 1 part of antioxidant RD and 1 part of antioxidant 4010 4 parts of sulfur was added to the open mill in turn, and kneaded at 40 ° C for 20 min. After the mixture was allowed to stand for 24 h, it was vulcanized on a flat vulcanizer, and the vulcanization conditions were 170 ° C for 16 min to obtain a three-dimensional graphene modified nitrile rubber composite. material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 7 parts of concentrated sulfuric acid, 0.7 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 80 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 180 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3) 100 parts of natural rubber, 3 parts of three-dimensional graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator TMTD and 1 part of accelerator CZ, 1.5 parts of antioxidant RD and 1 part of antioxidant 4010, 1 part of sulfur and 0.5 part of dicumyl peroxide were sequentially added to the open mill, kneaded at 55 ° C for 10 min, and the mixture was allowed to stand for 18 h, then vulcanized on a flat vulcanizer, and the vulcanization conditions were 150 ° C for 40 min to obtain three-dimensional graphite.
  • Ane modified natural rubber composite 100 parts of natural rubber, 3 parts of three-dimensional graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator TMTD and 1 part of accelerator CZ, 1.5 parts of antioxidant RD and 1 part of antioxidant 4010, 1 part of sulfur and 0.5 part of dicumyl peroxide were sequentially added to the open mill, kneaded at 55 °
  • Table 1 shows the performance parameters of the comparative test of the three-dimensional graphene-modified rubber composite prepared in Examples 1-8 and the rubber of Comparative Examples 1-4:
  • the preparation method of the present invention can greatly improve the electrical conductivity, strength, thermal conductivity and wear resistance of the rubber.

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Abstract

L'invention concerne un matériau composite caoutchouc modifié à base de graphène 3D comprenant en parties en poids : 100 parties de caoutchouc, 0,01 à 10 parties de graphène, 0,5 à 5 parties d'un agent de vulcanisation, et 8 à 12 parties d'agent de compoundage du caoutchouc. Ce matériau composite modifié à base de graphène 3D est considérablement amélioré en termes de conductivité électrique, de résistance à l'usure, de résistance à la chaleur et de performances de résistance par rapport à un caoutchouc existant, est simple à préparer et permet de mettre en oeuvre de manière aisée une production à grande échelle.
PCT/CN2017/098066 2016-08-22 2017-08-18 Matériau composite caoutchouc modifié à base de graphène 3d et son procédé de préparation WO2018036425A1 (fr)

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CN201610705206.3 2016-08-22
CN201610705206.3A CN106317505A (zh) 2016-08-22 2016-08-22 一种基于三维石墨烯改性的橡胶复合材料及其制备

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Cited By (7)

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